Processes for breaking petroleum emulsions



April 1951 r M. DE GROOTE EI'AL. 2,549,437

PROCESSES FOR BREAKING PETROLEUM EMULSIONS Filed Aug. 15, 1949 ALPHA TEIORPINEOL CaH4o loo/ |o04,

INVENTOR S,

MELVIN DE GROOTE,' ARTHUR F. W/RTEL, OWEN H. PETT' 5 mew? A TTORNEY Patented Apr. 17, 1951 PROCESSES FOR BREAKING PETROLEUM EMULSEONS Melvin De Groote, University City, and Arthur F. Wirtel and. Gwen H. Pettingill, Kirkwood, Mo., assignors to Petrolite Corporation, Ltd, Wilmington, DeL, a corporation of Delaware Application August 15, 1949, Serial No. 110,332

Claims.

This invention relates to processes or procedures particularly adapted for preventing, breaking or resolving emulsions of the water-in-oil type, and particularly petroleum emulsions.

Complementary to the above aspect of the invention herein disclosed is our companion invention concerned with the new chemical products or compounds used as the demulsifying agents in said aforementioned processes or procedures, as well as the application of such chemical compounds, products, or the like, in various other arts and industries, along with the method for manufacturing said new chemical products or compounds which are of outstanding value in demulsification. See our co-pending application Serial No. 199,793, filed August 11, 1949.

Our invention provides an economical and rapid process for resolving petroleum emulsions of the water-in-oil type, that are commonly referred to as cut oil, roily oil," emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

It also provides an economical and rapid process for separating emulsions which have been prepared under controlled conditions from mineral oil, such as crude oil and relatively soft waters or weak brines. Controlled emulsification and subsequent demulsification, under the conditions just mentioned, are of significant value in removing impurities, particularly inorganic salts, from pipeline oil.

. Demulsification, as contemplated in the present application, includes the preventive step of commingling the demulsifier with the aqueous component which would or might subsequently become either phase of the emulsion in the absence of such precautionary measure. Similarly, such demulsifier may be mixed with the hydrocarbon component.

Briefiy stated, the present process is concerned with the breaking of petroleum emulsions by means of certain glycol ethers of alpha-terpineol, and particularly in the form of cogeneric mixtures, as hereinafter described. These products are obtained by treatment of alpha-terpineol with ethylene oxide and propylene oxide within the limits hereinafter defined and with the proviso that all the propylene oxide is added first and then the ethylene oxide.

It is well known that a variety of compounds containing a reactive hydrogen atom, i. e., a hydrogen atom attached to oxygen, nitrogen, or

sulphur, will react with alkylene oxides, particularly ethylene oxide or propylene oxide, to yield the corresponding glycol or polyglycol derivative. Such oxyalkylated derivatives are readily prepared from chemical compounds in which the hydrogen atom is directly attached to oxygen, and particularly in the case of alcohols or phenols, such as aliphatic alcohols, phenols, alkylaryl alcohols, alicyclic alcohols, phenoxyalkanols, substituted phenoxyalkanols, etc. Generally speaking, it has been found advantageous to react a water-insoluble hydroxylated material, having 8 carbon atoms or more, with an alkylene oxide so as to introduce water solubility, or at least, significant or distinct hydrophile character, with the result that the derivative so obtained has surface-active properties.

Examples of suitable reactants of this type include octyl alcohol, decyl alcohol, dodecyl alcohol, tetradecyl alcohol, octadecyl alcohol, butylphenol, propylphenol, propylcresol, hexylphenol, octylphenol, nonylphenol, and cardanol, as Well as the corresponding alicyclic alcohols obtained by the hydrogenation of the aforementioned phenols. It has been suggested that at least some of such materials be used in the resolution of petroleum emulsions. As far as we are aware, none of such materials represent products which are acceptable in demulsification today from a competitive standpoint. In the majority of cases, such products are apt to be onesixth, one-fifth, one-fourth, or one-third as good as available demulsifying agents on the same percentage-of-active-material basis, or same cost basis.

In our co-pending application Serial No. 109,- 791, filed August 11, 1949, we stated as follows:

We have discovered a very few exceptions to the above general situation. For example, we have discovered, if one treats alpha-terpineol with ethylene oxide and propylene oxide so as to yield a cogeneric mixture of glycol ethers, that such mixed derivative has unusual properties, provided that the composition lies within a certain range, as hereinafter specified. A specific exemplification of this range is the product obtained by treating one mole of alpha-terpineol with 15 moles of propylene oxide, and then with 18 moles of ethylene oxide. Similarly, one may treat alpha-terpineol with the 18 moles of ethylene oxide first and then with the 15 moles of propylene oxide next.

In subsequent paragraphs from time to time reference is made to compounds or cogeneric mixtures. A first glance, it may appear that such language is indefinite, and, perhaps, contradictory. It is the intention at the moment only to point out that there is no inconsistency in such description, and that, subsequently, there will be a complete explanation of why such designation is entirely proper.

The cogeneric mixtures of glycol ethers of alpha-terpineol so obtained are unusually effective demulsifying agents on a comparatively small number of oil field emulsions, which, oddly enough, appear rather widely distributed geographically. These alpha-terpineol ether mixtures do not appear to be universally competitive, and, as a matter of fact, appear to be highly selective in regard to their action as demulsifying agents. However, such products have significant utility in a number of different oil fields, where they serve better than any other available demulsifying agent. Their utility may, of course, increase as time goes on.

It is very peculiar that the efiectiveness of the demulsifying agents herein described seems to be limited to a very narrow range or area as far as composition goes. Reference is made to the accompanying drawing, in which there is presented a triangular graph showing the composition of certain glycol ethers of alphaterpineol or cogeneric mixtures thereof, derivable from alpha-terpineol and ethylene oxide alone, or alpha-terpineol and propylene oxide alone, or alpha-terpineol and both propylene oxide and ethylene oxide, in terms of the initial reactants. We have found that effective demulsifying agents lie approximately within a small and hitherto unsuspected area indicated by the trapezoid determined by the points 8, 9, and 11. More specifically, particularly effective demulsifying agents appear within a smaller range, as set forth approximately by the area indicated by the segment of a circle in which the area of the segment is limited to derivatives in which alpha-terpineol contributes at least 4% by weight of the ultimate compound, or cogeneric mixture.

The circle itself is identified by the fact that the points i, 3 and. 6 appear on the circle. The more effective of these better compounds or cogeneric mixtures are those which appear within the triangle which represents part of the circle and part of the segment, to wit, the triangle identified by the points 1, 3 and 6. The most effective compounds or cogeneric mixtures of all are those which fall within the inner central triangle of the larger outer triangle identified by the points 1, 3 and 6, to wit, the smaller triangle identified by the points 2, i and 5. The most outstanding of these effective compounds or cogeneric mixtures is the one which appears to fall substantially at the center of the smaller triangle identified by point 7. This particular point is obtained by treating one mole of alphaterpineol with moles of propylene oxide, followed by treatment with 18 moles of ethylene oxide.

In spite of the unique character of the compounds or cogeneric mixtures previously described we have made additionally an invention within an invention. This can be illustrated by reference to the compounds or cogeneric mixtures whose composition is determined by the inner triangle 2, 4, 5. This preferred class of derivatives, or, for that matter, all the herein described products, can be made in three different ways: (a) by adding propylene oxide first and then ethylene oxide, (12) by adding ethylene oxide first and then propylene oxide, or (c) by adding the two oxides by random, indifferent, or uncontrolled addition so as to produce a polyglycol ether in which the propylene radicals and ethylene radicals do not appear in continuous succession, but are heterogeneously distributed.

The attached drawing is that of a conventional graph for representation of proportions of constitnents of three component compositions wherein the proportions of each may vary from zero to Compositions which have the three constituents present in such proportions as to fall within the area 8, 9, l0 and l l are those the use of which is claimed in our application Serial No. 199,791. Compositions which have the three constituents present in such proportions as to fall within the segment of the circle formed by the chord 3, 5, 6 and including the points i 2, i and l and with the proviso that the alpha-terpineol is reacted first with all the propylene oxide and then with all the ethylene oxide, are those the use of which is claimed in this application.

The present invention represents the invention within the invention referred to in our aforementioned co-pending application Serial No. 109,- 791, filed August 11, 1949. We have found that much more effective demulsifiers are obtained by adding propylene oxide first, and subsequently adding ethylene oxide, other than some other procedure, su h as adding ethylene oxide first and then propylene oxide or a mixed addition. This is particularly true in regard to the compositions coming within the segment of the circle previously referred to in Figure 1.

As an illustration of the preparation of various compounds or cogeneric mixtures, and particularly the most desirable ones, and also those which are helpful in setting the limits in the graph previously referred to, the following examples are included: In connection with these examples it will be noted that the oxyalkyiation of alpha-terpineol, i. e., by treatment with ethylene oxide or propylene oxide or a mixture of the two, is conventional. The procedure is conducted in the same manner employed in connection with other aicohols, or the like, and generally, an alkaline catalyst is employed. See, for example, U. S. Patent No. 2,440,093, dated April 20, 1948, to Israel, and British Patent No. 602,591, applied for February 12, 1945.

Example 1 The reaction vessel employed was a stainless steel autoclave with the usual devices for heating, heat-control, stirrer, inlet, outlet, etc., which is conventional in this type of apparatus. The capacity was approximately 40 gallons. The stirrer operated at a speed of approximately 250 R. P. M. There were charged into the autoclave 15.4 pounds .of alpha-terpineol. There were then added 12 /2 ounces (approximately 5% by weight) of ground caustic soda. The autoclave was sealed, swept with nitrogen gas, and stirring started immediately and heat applied, and the temperature allowed to rise to approximately C. At this point addition of propylene oxide was started. It was added continuously at such speed that it was absorbed by the reaction as rapidly as added. The amount of propylene oxide added as 88. pounds. The time required to add this propylene oxide was Slightly in excess of one hour, about 1 hours. During this time the temperature was maintained at 150 to C., using cooling water through the inner coils when necessary, and otherwise applying heat, if required. At the 5 end of the addition of the propylene oxide there was added ethylene oxide, as previously indicated. The amount of ethylene oxide added was 80 pounds. The temperature employed, and operating conditions, were the same as with the addition of propylene oxide. It is to be noted, however, that ethylene oxide appears to be more reactive and the reaction seems to require a greater amount of cooling water to hold the tem- 6 fully because there is an obvious hazard in handling a large quantity of material in an autoclave which is not necessarily present in the use of a small vessel.

The following table includes a series of compounds or cogeneric mixtures which have been selected as exemplifying the herein included products.

The data are summarized in the following table:

Alpha Terpineol Propylene Oxide Ethylene Oxide Point on graph EX NO Weight Weight Weight identifying Weight Mom} Per Cent, Weight MOW Per Cent, Weight M0131 Per Cent, specific Used, in in Final Used, in f in Final Used, in Ratio in Final Glycol Grams Glycol Grams Glycol Grams Glycol Ether Ether Ether Ether A 154 1. 15.0 462 7. 96 45 411 9. 34 40 1 B.-. 154 1.0 10.0 771 13.3 50 615 14.0 40 2 C 154 1. O 5.0 1, 700 29. 3 55 1, 232 2b. 0 4O 3 D 154 1. 0 10.0 693 ll. 95 45 693 15. 77 45 4 E 154 1.0 5.0 1,542 26. (i 50 1,390 31. 6 45 5 F. 154 1. 0 5. O 1, 390 23. 95 45 1, 542 35.10 50 6 G 154 l. 0 8. 45 866 14. 95 47. 55 800 18. 17 44 7 H 154 l. O 9. 2 812 14. 0 48. 6 704 16.0 43. 2 I 154 1. 0 9. 0 812 14. 0 47. 4 748 17.0 43. 6 .T 154 1. 0 8. 8 812 14.0 46. 2 792 18. 0 45.0 K 154 l. 0 h. 7 870 15.0 49. 0 748 17. 0 43. 3 G 154 1. 0 8. 45 866 14. 9G 47. 55 800 18. 17 44 2 7 L. 154 1. 0 8. 3 870 15. 0 46. 7 S36 19. 0 45. 0 M 154 1. 0 8. 2 934 16. 0 40. o 792 18. 0 42. 3 N 154 1. 0 8. 0 93-4 16. 0 4S. 5 P536 19. O 43. 5 O 154 1.0 7.8 934 16.0 47.4 880 20.0 44.5

1 With n inner triangular area.

2 Duplicated for convenience.

perature range indicated. The time required to add the ethylene oxide was about the same, or slightly less, usually just a little more than an hour.

During the addition of the oxides the pressure was held at approximately 50 pounds per square inch gauge pressure, or less. When all the oxide had been added (ethylene oxide being the final addition in this particular instance) the autoclave was permitted to stay at the same temperature range for another half hour, even longer, if required, or until the gauge pressure had been reduced to zero, or substantially zero, indicating the reaction was complete. The final product was an oily material, somewhat viscous in nature, resembling castor oil and having a definite alphaterpineol or terpene-like odor. It was soluble in water and also soluble in non-aqueous solvents, such as aromatic hydrocarbons, and others, although not soluble in some non-polar hydrocarbon solvents. The final yield was substantially the total weight of the initial reactants.

Example 2 The same procedure as in Example 1, preceding, was conducted on a laboratory scale employinga small autoclave having a capacity of approximately one liter, up to a 5 gallon size. The amount of terpineol employed was 46.2 grams, the amount of propylene oxide employed was 259.8 grams, and the amount of ethylene oxide employed was 240 grams. The amount of caustic soda used as a catalyst was 2.33 grams. The operating conditions were substantially the same as on a larger scale. Actually, the reaction seemed to go faster in the small autoclave, and the time of absorption could be reduced, if desired. In many instances absorption would take place in the laboratory autoclave in a fraction of the time required in the larger autoclave; in fact, in many instances absorption was complete in 5 to or minutes, as compared to one hour on a larger scale. Needless to say, on a large scale, addition must be conducted care- In the preparation of the above compounds the alkaline catalysts used was either flake caustic soda finely ground with mortar and pestle, or powdered sodium methylate, equivalent to 5% by weight of the alpha-terpineol which was employed.

For reasons which are pointed out hereinafter in greater detail, it is substantially impossible to use conventional methods and obtain a single glycol ether of the kind described. Actually, one obtains a cogeneric mixture of closely related or touching homologues. These materials invariably have high molecular weight and cannot be separated from one another by any known method without decomposition. The properties of such mixture represent the contribution of the various individual members of the mixture.

Although one cannot draw a single formula and say that by following such and such procedure, one can obtain or or of such single compound, yet one can readily draw the formulas of a large number of compounds which appear in some of the mixtures described elsewhere, or can be prepared readily as components of mixtures which are manufactured conventionally. Such formulas, representing significant portions of various mixtures, are of distinct value, insofar that they themselves characterize the invention, i. e., describe individual components which are typical of the members of the cogeneric mixture. In the following formulas since ROI-I can represent alpha-terpineol, R0 is the ether radical obtained from alphaterpineol by removal of the hydrogen atom attached to the oxygen atom.

subjects such compound to oxyalkylation, such as oxyethylation, or oxypropylation, it becomes obvious that one is really producing a polymer of the alkylene oxide except for the terminal group. This is particularly true where the amount of oxide added is comparatively large, for instance, 10, 20, 30, 40, or 50 units. If such a compound is subjected to oxyethylation so as to introduce 30 units of ethylene oxide, it is well known that one does not obtain a single constituent, which, for the sake of convenience, may be indicated as RO(C2H4O)30H. Instead, one obtains a cogeneric mixture of closely related homologues in which the formula may be shown as the following: RO(C2H4O)nI-I, wherein n, as far as the statistical average goes, is 30, but the individual members present in significant amount may vary from instances where n has a value of 25 and perhaps less, to a point where n may represent 35 or more. Such mixture is, as stated, a cogeneric, closely related series of touching homologous compounds. Considerable investigation has been made in regard to the distribution curves for linear polymers. Attention is directed to the article entitled Fundamental principles of condensation polymerization, by Paul J. Flory, which appeared in Chemical Reviews, Vol. 39, No. 1, page 137.

Unfortunately, as has been pointed out by Flory and other investigators, there is no satisfactory method, based on either experimental or mathematical examination, of indicating the exact proportion of the various members of touching homologous series which appear in cogeneric condensation products of the kind described. This means that from the practical standpoint, i. e., the ability to describe how to make the product under consideration and how to repeat such production time after time without difiiculty, it is necessary to resort to some other method of description.

Actually, from a practical standpoint, it is much more satisfactory, perhaps, to describe the ultimate composition in terms of the reactants. i. e., alpha-terpineol and the two alkylene oxides. The reason for this statement is the following: If one selects a specific compound, it must be borne in mind that such compound is specific only insofar that the cogeneric mixture in terms of a statistical average will conform to this formula. This may be illustrated by an example such as RO(C3II60)15 C2H-O)18H If one m.- bines reactants in the predetermined weight ratio so as to give theoretically this specific component and assuming that only one chemical compound were formed, what happens is that, although this particular compound may be present in a significant amount and probably less than 50%, actually one obtains a cogeneric mix ture of touching homologues in which the statistical average does correspond to this formula. For instance, selecting reactants, which, at least theoretically, could give the single compound what actually happens is that one obtains a sort of double cogeneric mixture, for the reason that in each batch or continuous addition of an alkylene oxide, a cogeneric mixture is formed. Since the present products require the addition of at least two difierent multi-molar proportions of each of two different alkylene oxides (ethylene oxide and propylene oxide) it becomes obvious that a rather complex cogeneric mixture must result.

8 This can be best illustrated by example. Assume that one is going to use the indicated ratio. to wit, one pound mole of alpha-terpineol,

15 pound moles of propylene oxide, and 18 pound o moles of ethylene oxide. The initial step involves the treatment of one pound mole of alpha-terpineol with 15 pound moles of propylene oxide so as to yield theoretically RO(C3l-I6O-)15H; actually, as pointed out, one does not obtain R0 (CSHGO) H in which n is 15, but really one obtains a cogeneric mixture in which there are present significant amounts of homologues in which it varies from 16, ll and 12, on up to 17, 18 and possibly 19 or 20. A statistical average, however, must, of course, correspond to the proportion of the initial reactants, i. e., a compound of the formula RO(C3H60)15H which is present undoubtedly to a significant extent.

When this cogeneric mixture is then subjected to reaction with 18 moles of ethylene oxide, it becomes obvious that, although one may obtain some RO C3H60 15 C2H40 18H, yet this particular product can only be present to a minor extent for reasons which have been described in connection with oxyethylation and which now are magnified to a greater degree by oxypropylation. Stated another way, it is probable that the cogeneric mixture represents something like in which, as previously pointed out, components resent in important percentages are those in which n could vary from anywhere beginning with 153 to 12, on up to 18, to 20. By the same token, components present in important percent- "C are those in which it could vary anywhere in 13 or 1; up to the lower 20s, such as 21, 22, Indeed, homologues of a lower or er value of n a :d n will be present in minor age of such components de the further removed they are from the average composition. However, in spite of such variation in regard to the cogeneric mixture, the ultimate composition, based on the ingredients. which enter into it and based on the statistical average of such constituents, can still be expressed by the formula then the constituents are added. in actual molar proportions, based on whole numbers. If, however, one selects a point in the inner triangular area, which, when recalculated in terms of molar proportions, produces a fractional number, there is still no reason why such proportion of initial reactant should not be adopted. For instance, one might select a point in the triangular graph, which, when calculated in terms of molecular proportions, represents a formula, such as the following: RO(C3H60 15.5(C2I-I40)18H. This, of course, would be immaterial, for the reason that if one starts with a pound mole of alpha-terpineol and adds 15.5 pound moles of propylene oxide,

one will obtain, on the average, a mixture closely comparable to the one previously described, using exacty 15 pound moles of propylene oxide instead of 15.5. Such mixture corresponds to the compound RO(CsI-IsO)1s.s only in the sense of the average statistical value, but not in the sense that there actually can be a compound corresponding to such formula. Further discussion of this factor appears unnecessary in light of what has been said previously.

Such mixture could, of course, be treated with 18 pound moles of ethylene oxide. Actually, all that has been said sums up to this, and that is, that the most satisfactory way, as has been said before-of indicating actual materials obtained by the 'usual and conventional oxyalkylation process is in terms of the initial reactants and it is obvious that any particular point on the triangular graph, from a practical aspect, invariably and inevitably represents the statistical average of seve"al or possibly a dozen or more closely related cogeners of almost the same composition, but representing a series of touching homologues. The particular point selected represents at least the composition of the mixture expressed empirically in the terms of a compound representing the statistical average.

Previous reference has been made to the fact that comparatively few oxyalkylated derivatives of simple hydroxylated compounds find utility in actual demulsification practice. We have pointed out that we have found a very few exceptions to this rule. The fact that exceptions exist, as in the instant-invention, is still exceedingly diificult to explain if one examines the slight contribution that the end group, derived from the hydroxylated material, makes to the entire compound. Referring for the moment to a product of the kind which has been described and identified by the formula RO (CsHsO) 15(C2H4O) 18H it becomes apparent that the molecular weight is in the neighborhood of 1890 and actually the alpha-terpineol contributes less than 10% of the molecular weight. As a matter of fact, in other comparable compounds the alpha-terpineol may contribute as little as 4% or 5% and yet these particular compounds are effective demulsifiers. Under such circumstances, it would seem reasonable to expect that some other, or almost any other, cyclic 6-carbon atom compound comparable to alpha-terpineol would yield derivatives equally effective. Actually, this is not the case. We know of no theory or explanation to suggest this highly specific nature or action of the compound or cogeneric 'mixture derived from alpha-terpineol.

As has been pointed out previously, for some reason which we do not understand and for which we have not been able to offer any satisfactory theory, we have found that the best compounds, or, more properly, cogeneric mixtures, are obtained when all the propylene oxide is added first and then all the ethylene oxide is added; Although this is true to at least some extent in regard to all the compositions Within the trapezoidal area in the triangular graph, yet it is particularly true if the composition comes within the segment of the circle previously referred to in the drawing. In such event, one obtains a much more effective demulsifier than by any other combination employing ethylene oxide alone, propylene oxide alone, or any variation in the mixture of the two, as illustrated by other formulae. In fact, the compound or cogeneric mixture so obtained, as far as demulsification is concerned, is not infrequently at least one-third better than any other derivative obtained in the manner described involving any of the other above Variations.

The significance of what has been said previously becomes more emphatic when one realizes that, in essence, we have found that one isomer is a more effective demulsifying agent than another isomer. The word isomer is not exactly right, although it is descriptive for the purpose intended, insofar that We are not concerned with a single compound, but with a cogeneric mixture which in its statistical average corresponds to such compound. Stated another way, if we start with one pound mole of alpha-terpineol, 15 pound moles of propylene oxide and 18 pound moles of ethylene oxide, we can prepare two different cogeneric mixtures, which, on a statistical average, correspond to the following:

R0 (Cal-I40) 18 (0on0) 15H and There is nothing we know which would suggest that the latter be a much more effective demulsifying agent than the former and also that it be more effective for other industrial purposes. The applicants have had wide experience with a wide variety of surface-active agents, but they are unaware of any other similar situation, with the exception of a few instances which are the subject-matter of other co-pending applications, or under investigation. This feature represents the invention within an invention previously referred to, and is the specific subject-matter of the instant application. As to the aspect concerned with the composition broadly, as differentiated from the demulsification process, see our copending application Serial No. 109,793, filed August 11, 1949.

Reference has been made to thefact that the product herein specified, and particularly for use as a demulsifier, represents a cogeneric mixture of closely related homologues. This does not mean that one could not use combinations of such cogeneric mixtures. For instance, in the previous table data have been given for preparation of cogeneric mixtures which statistically correspond, respectively, to points I, 3 and 6. Such three cogeneric mixtures could be combined in equal weight so as to give a combination in which the mixed statistical average would correspond closely to point I.

Similarly, one could do the same thing by preparing cogeneric mixtures corresponding to points 2, and 5, described in the previous table. Such mixtures could then be combined in equal parts by weight to give another combination which would closely correspond on a mixed statistical basis to point 1. Nothing said herein is intended to preclude such combinations of this or similar type.

Throughout this specification, reference has been made to alpha-terpineol. We have employed a commercial product sold by the Hercules Powder Company under the designation of Terpineol 318 which consist of alpha-terpineol and 15% beta terpineol. This mixture melts sufficiently low for the product to be a liquid at ordinary temperatures, whereas, alpha-terpineol is a, mushy crystalline product which is somewhat more dimcult to handle. Terpineol 318 is also approximately one cent a pound cheaper ll 1 than alpha-ter.pineol. It is understood that wherever we have specified alpha-terpineol, this particular product can be employed. This, of course, is obvious, for the reason that, if desired, one can mix alpha-terpineol with some other product susceptible to oxyethylation and oxypropylation, such as menthylcyclohexanol, and subject the two products to simultaneous oxyalkylation. For a number of reasons, it is ordinarily desirable to use a procedure in which only one product is reacted at a time.

At times we have examined samples of Terpineol 318 which appeared acidic, due to the presence apparently of a resinic acid. Attempt to oxyalkylate causes difiiculty, because the alkaline catalyst is neutralized. In such cases the acidity should be neutralized and then the customary amount of catalyst added.

It is possible that the oxyalkylation, particularly oxypropylation, of Terpineol 318 is a bit slower than that of straight alpha-terpineol, due to the presence of beta-terpineol. In our copending applications Serial Nos. 109,734, 109.795, 109,796, and 109,797, all filed August 11, 1949, we have pointed out that the oxypropylation, for example, of beta-terpineol, was slower than that of alpha-terpineol.

Conventional demulsifying agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent, such as water, petroleum hydrocarbons, such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols, particularly aliphatic .alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneous solvents, such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc., may

be employed as the demulsifying agent of our process may be admixed with one or more of the solvents customarily used in connection with conventional demulsifying agents. Moreover, said material or materials may be used alone or in admixture with other suitable well-known classes of demulsifying agents.

It is well known that conventional demulsifying agents may be used in a water-soluble form, or in an oil-soluble form, or in a form exhibiting both oil and water-solubility. Sometimes they may be used in a form which exhibits relatively limited oil-solubility. However, since such reagents are frequently used in a ratio of 1 to 10,000, or 1 to 20,000, or 1 to 30,000, or even 1 to 40,000, or 1 to 50,000, as in desalting practice, such an apparent insolubility in oil and water is not sig nificant, because said reagents undoubtedly have solubility within such concentrations. This same fact is true in regard to the material or materials employed as the demulsifying agent of our process.

In practising our process for resolving petroleum emulsions of the water-in-oil type, a treating agent or demulsifying agent of the kind above described is brought into contact with or caused to act upon the emulsion to be treated, in any of the various apparatus now generally used to resolve or break petroleum emulsions with a chemical reagent, the above procedure being used alone or in combination with other demulsifying prosion is admixed with the demulsifier, for example by agitating the tank of emulsion and slowly dripping demulsifier into the emulsion. In some cases mixing is achieved by heating the emulsion. while dripping in the demulsifier, depending upon the convection currents in the emulsion to produce satisfactory admixture. In a third modification of this type of treatment, a circulating pump withdraws emulsion from, e. g., the bottom of the tank, and l e-introduces it into the top of the tank, the demulsifier being added, for example, at the suction side of said circulating pump.

In a second type of treating procedure, the demulsifier is introduced into the well fluids at the well-head or at some point between the well-head and the final oil storage tank, by means of an adjustable proportioning mechanism or proportioning pump. Ordinarily the flow of fluids through the subsequent lines and fitting suffices to produce the desired degree of mixing of demulsifier and emulsion, although in some instances additional mixing devices may be introduced into the flow system. In this general procedure, the system may include various mechanical devices for withdrawing free water, separating entrained water, or accomplishing quiescent settling of the chemicalized emulsion. Heating devices may likewise be incorporated in any of the treating procedures described herein.

A third type of application (down-the-,hole) .of demulsifier to emulsion is to introduce the demulsifier either periodically or continuously in diluted or undiluted form into the well and to allow it to come to the surface with the well fluids, and then to flow/the chemicalized emulsion through any desirable surface equipment, such as employed in the other treating procedures. This particular type of application is decidedly useful when the demulsifier is used in connection with acidification of calcareous oilbearing strata, especially if suspended in or dissolved in the acid employed for acidification.

In all cases, it will be apparent from the foregoing description, the broad process consists simply in introducing a relatively small proportion of demulsiiier into a relatively large proportion of emulsion, admixing the chemical and emulsion either through natural flow or through special apparatus, with or without the application of heat, and allowing the mixture to stand quiescent until the undesirable water content of the emulsion saparates and settles from the mass.

The following a typical installation:

A reservoir to hold the demulsifier of the kind described (diluted or undiluted) is placed at the well-head where the efiiuent liquids leave the well. This reservoir or container, which may vary from 5 gallons to 50 gallons for convenience, is connected to a proportioning pump which injects the demulsifier drop-wise into the fluids leaving the well. Such chemicalized fluids pass through the fiowline into a settling tank. The ettling tank consists of a tank or" any convenient size, "for instance, one which will hold amounts of fluid produced in 4 to 24 hours (500 barrels to 2000 barrels capacity), and in which there is a perpendicular conduit from the top of the tank to almost the very bottom so as to permit the incoming fluids to pass from the top of the settlin tank to the bottom, so that such incoming fluids do not disturb Stratification which takes place durin the course of demulsification. The settling tank has two outlets, one being below the water level to drain off the water resulting from demulsification or accompanying the emulsion as free water, the other being an oil outlet at the top to permit the passage of dehydrated oil to a second tank, being a storage tank, which holds pipeline or dehydrated oil. If desired, the conduit or pipe which serves to carry the fluids from the well to the settling tank may include a section of pipe with baiiles to serve as a mixer, to insure thorough distribution of the demulsifier throughout the fluids, or a heater for raising the temperature of the fluids to some convenient temperature, for instance, 120 to 160 F., or both heater and mixer.

Demulsification procedure is started by simply setting the pump so as to feed a comparatively large ratio of demulsifier, for instance, 1:5,000. As soon as a complete break or satisfactory demulsification is obtained, the pump is regulated until experience shows that the amount of demulsifier being added is just sufficient to produce clean or dehydrated oil. The amount being fed at such stage is usually 1:10,000, 1 15,000, 1 :20,000, or the like.

In many instances the oxyalkylated products herein specified as demulsifiers can be conveniently used without dilution. However, as previously noted, they may be diluted as desired with any suitable solvent. For instance, by mixing 75 parts by weight of an oxyalkylated derivative, for example, the product of Example 1, with 15 parts by weight of xylene and 10 parts by weight of isopropyl alcohol, an excellent demulsifier is obtained. Selection of the solvent will vary, depending upon the solubility characteristics of the oxyalkylated product, and of course, will be dictated in part by economic considerations, i. e., cost.

As noted above, the products herein described may be used not only in diluted form, but also may be used admixed with some other chemical demulsifier. For example, a mixture which exemplifies such combination is illustrated by the following:

Oxyalkylated derivative, for example, the product of Example 1,

A cyclohexylamine salt of a. polypropylated naphthalene monosulfonic acid, 24%;

An ammonium salt of a polypropylated naphthalene inono-sulfonic acid, 24%;

A sodium salt of oil-soluble mahogany petroleum sulfonic acid, 12%;

A high-boiling aromatic petroleum solvent, 15%;

Isoproply alcohol, 5%.

The above proportions are all weight percents.

The highly specific nature of the present invention is emphasized by the following fact. If alpha-terpineol is first subjected to moderate hydrogenation so as to eliminate the unsaturation and convert the product into dihyclro-alphaterpineol, and if dihydro-alpha-terpineol is employed to replace a1pha-terpineol in the preparation of the herein described derivatives, we have found such products to show a difierent solubility character; and what is more important, to be without any significant value for one of the most important purposes for which such derivatives can be employed, to wit, the demulsification of petroleum emulsions of the water-in-oil type.

Throughout the specification elsewhere, reference has been made to homologues. It is quite likely that it would be equally proper in numerous instances and perhaps in all the herein described products, to refer to isomers as well as homo- 14 logues. The reason for this statement is that propylene oxide, as differentiated from ethylene oxide, can, at least theoretically, combine with a hydroxylated material ROI-I to give two different derivatives, one being aprimary alcohol and the other a secondary alcohol. This is illustrated by the following:

E H ROH no-c on3 ROC- -011rt 3 n ROH Ho o om Elsewhere in the specification the word isomer has been used thus: isomer. It is not believed there is any confusion between such terminology in that particular instance and what is said immediately preceding.

Attention is directed to the fact that the herein described compounds, compositions and the like which are particularly adapted for use as demulsifiers for water-in-oil emulsions, as found in the petroleum industry are hydroxylated derivatives, i. e., carry or include a terminal hydroxyl radical as part of their structure. We have found that if such hydroxylated compound or compounds are reacted further so as to produce entirely new derivatives, such new derivatives have the properties of the original hydroxylated compound, insofar that they are effective and valuable demulsifying agents for resolution of waterin-oil emulsions, as found in the petroleum industry, as breakinducers in doctor treatment of sour crude, etc.

Such hydroxylated compounds can be treated with various reactants, such as glycide, epichlorohydrin, dimethyl sulfate, sulfuric acid, maleic anhydride, ethylene imine, etc. If treated with epichlorohydrin or monochloroacetic acid, the resultant product can be further reacted with a tertiary amine, such as pyridine, or the like, to give quaternary ammonium compounds. If treated with maleic anhydride to give a total ester, the resultant can be treated with sodium bisulfite to yield a sulfosuccinate. Sulfc groups can be introduced also by means of a sulfating agent, as previously suggested, or by treating the chloroacetic acid resultant with sodium sulfite.

However, the class of derivatives most readily prepared in wide variety are the esters of monocarboxy and polycarboxy acids.

Assuming a typical derivative which can be indicated thus:

RO C3EI6O 21 C2H4O)WH the ester of the monocarboxy acid is as follows:

RO(C H O)n(CZH O)"'( JR The acid ester of a dicarboxy acid is as follows:

0 R0 canton o2Hio R"-a" o00H The complete ester of a dicarboxy acid is as follows:

The chloroacetic acid ester is as follows:

The quaternary compound obtained b reacting the above mentioned product with pyridine is as follows:

l no 031160 cmimbdcum Among the various kinds of monocarboxy acids suitable for preparation of esters are the alphahalogen monocarboxylic acids having not over 6 carbon atoms. Typical acids exemplifying this class are chloroacetic acid, dichloroacetic acid, bromoacetic acid, alpha-bromobutyric acid, etc. Needless to say, in this instance and all others where reference is made to the acid, the functional equivalent, such as the acylchloride, the anhydride, the ester, the amide, etc., may be employed.

Another class of esters are those obtained from certain drastically-oxidized hydroxyacetylated castor oil fatty acids. The dra tically-oxidized acetylated ricinoieic acid compounds are employed to furnish the acyl radical of the ester. In this particular instance, as in all other instances, one may prepare either a total ester or a partial ester, and when carboxy .acids are employed, one may have not only partial esters which have residual hydroxyl radicals or re idual carboxy radicals, but also partial esters in which both are present.

A somewhat similar type of ester is obtained from hydroxylacetylated drastically-oxidized castor oil fatty acids. It is to be pointed out that hydroxyacetylation may take place first, and drastic oxidation subsequently, or the reverse may be true, or both procedures may be conducted simultaneously. In any event, such products supply acyl radicals of one type of ester herein included.

Another somewhat similar class are esters ob tained from hydroxyacetylated drastically-oxidized dehydrated ricinoleic acid. in this class ricinoleic acid, castor oil, or the like, is subjected to dehydration as an initial step. Such products may be employed to supply the acyl radical of one type of ester herein included.

Another type of ester which may be employed is a sulfo-iatty acid ester, in which there is present at least 8 and not more than 22 carbon atoms in the fatty acid radical. The sulfo-radical includes both the acid sulfonates and the sulfonic acids. Briefly stated, suitable sulfo acids herein employed as reactants are sulio-oleic, sulfo-ricinoleic, sulfo-aromatic fatty acids obtained, for example, from benzene, toluene, xylene, etc., and oleic acid 01' some other unsaturated acid.

Another class of acids are polycarboxy acids, such as commonly used in forming plasticizers, polyester resins, etc. One may use a tricarboxy acid, such as tricarballylic acid, or citric acid, but our preference is to employ a dicarboxy acid, or acid anhydride, such as oxalic acid, maleic acid, tartaric acid, citraconic acid, phthalic acid, adipic acid, succinic acid, azelaic acid, sebacic acid, adduct acids obtained by reaction between maleic anhydride, citraconic anhydride, and butadiene, diglycollic acid, or cyclopentadiene. Oxalic acid is not quite as satisfactory as some 01"- the other acids, due to its tendency to decompose. In light of raw material costs, it is our preference to use phthalic anhydride, maleic anhydride, citraconic anhydride, diglycollic acid, adipic acid and certain other acids in the same price range which are both cheap and heat-re- 16 sistant. One may also use adduct acids of the diene orv Clocker type.

Another class of esters are derived from certain high molal monocarboxy acids. It is well known that certain monocarboxy organic acids containing 8 carbon atoms or more, and not more than 32 carbon atoms, are characterized by the fact that they combine with alkalies to produce soap or soap-like materials. These detergent-forming acids include fatty acids, resin acids, petroleum acids, etc. For the sake of convenience, these acids will be indicated by the formula RCOOl-i. Certain derivatives of detergent-forming acids react with alkali to produce soap or soap'like materials and are the obvious equivalent of the unchanged or unmodified detergentforming acids. For instance, instead of fatty acids, one might employ the chlorinated fatty acids. Instead of the resin acids, one might employ the hydrogenated resin acids. Instead of naphthenic acids, one might employ brominated naphthenic acids, etc. I

The fatty acids are of the type commonly referred to as higher fatty acids; and, of course, this is also true in regard to derivatives of the kind indicated, insofar that such derivatives are obtained from higher fatty acids. The petrole um acids include not only naturally-occurring naphthenic acids, but also acids obtained by the oxidation of wax, parafiin, etc, Such acids may have as many as 32 carbon atoms. For instance, see U. S. Patent No. 2,242,837, dated May 20, 1941, to Shields.

The monocarboxy detergent-forming esters of the oxyalkylated derivatives herein described, are preferably derived from unsaturated fatty acids having 18 carbon atoms. Such unsaturated fatty acids include oleic acid, ricinoleic acid, linoleic acid, etc. One may employ mixed fatty acids, as, for example, the fatty acids obtained from hydrolysis of cottonseed oil, soyabean oil, etc. It is our ultimate preference that the esters of the kind herein contemplated be derived from unsaturated fatty acids, and more especially, unsaturated fatty acids containing a hydroxyl radical, or unsaturated fatty acids which have been subjected to oxidation. In addition to synthetic carboxy acids obtained by the oxidation of parafiins or the like, there is the somewhat analogous class obtained by treataing carbon dioxide or carbon monoxide, in the presence of hydrogen or an olefine, with steam, or by causing a halogenated hydrocarbon to react with potassium cyanide and saponifying the product obtained. Such products or mixtures thereof, having at least 8 and not more than 32 carbon atoms, and having at least one carboxyl group or the equivalent thereof, are suitable as detergent-forming monocarboxy acids; and another analogous class equally suitable is the mixture of carboxylic acids obtained by the alkali treatment of alcohols of high molecular Weight formed in the catalytic hydrogenation of carbon monoxide.

One may have esters derived not only from a single class of acids of the kind described, but also from more than one class, i. e., one may employ mixed esters such as esters obtained, for example, from high molal detergent-forming acids having 8 to 22 carbon atoms, as previously described, in combination with acids of the alpha-halogen carboxy type having less than 8 carbon atoms, such as chloroacetic acid, bromoacetic acid, etc., as previously described.

Drastically-oxidized oil, such as drasticallyoxidized castonoil, r dras'tic ally dxidi z ed dehydratedcastor oil, may be employed to supply-the acyl radical. In order instances, One may produce mixed esters-by using polycarboxy acids, such as phthalic, acid, .diglycollic acid, etc., in combination with detergent-forming acids, such as oleic acid, stearic acid, naphthenic acid, etc.

Other carboxy .acidsmaybe employed in which there is also a sulfa group present,1such'as sulfoiphthalic, sufo-benzoic, sulfo-succinic, etc. Esters may be obtained from low molal hydroxylated acids having less than 8 carbon atoms, such as hydroxyacetic acid, lactic acid, etc. Similarly, one may employ low molal aliphatic acids having less than 8 carbon atoms, such as acetic acid, butyric acid, etc. Similarly, one may employ low molal acids having the vinyl radical, such as acrylic acid, methacrylic acid, crotonic acid, etc. It will be noted that these acids contain various numbers of acyl radicals varying generally up to 22 carbon atoms for the monocarboxy acids, and as many as 36 carbon atoms in the case of certain polycarboxy acids, particularly the dimer obtained by the dimerization of 9,11-octadecadienic acid. As to this particular product, see U. S. Patent No. 2,347,562, dated April 25, 1944, to Johnston.

Other suitable acids are cyclic monocarboxy acids having not over 32 carbon atoms. Examples of such acids include cyclohexane acetic acid, cyclohexane butyric acid, cyclohexane propionic acid, cyclohexane caproic acid, benzoic acid, salicylic acid, phenoxy acetic acid, etc.

The preparation of such esters are conventional and do not require elaborate description. Generally speaking, our procedure is to react the appropriate amount of a selected hydroxylated compound with the free acid in presence of a high boiling solvent, such as xylene, using 1% or 2% of para-toluene sulfonic acid along with a phaseseparating trap until the amount of water indicates the reaction is complete, or substantially complete. The time required is usually 4 to 20 hours. Such esters are, as previously stated, very effective for resolution of water-in-oil emulsions, as found in the petroleum industry.

The triangular graph represents the three-component system. Using 4 reactants, i. e., the three depicted in the triangular graph plus glycide, gives a four-reactant system which yields derivatives at least equal for demulsification of water-in-oil emulsions to those herein described. The use of glycide in a fourcomponent reactant permits unusual structure, as, for example, a variety of furcation. Thus, the hydroxlyated initial reactant can be treated with glycide in the conventional manner, using an alkaline catalyst and after an introduction of a mo-le-for-mole ratio of glycide, then propylene oxide can be introduced in the manner previously described, and thereafter ethylene oxide can be added. If desired, the propylene oxide can be introduced first and then one mole of glycide added, followed by ethylene oxide, or both procedures can be employed.

Moreover, glycide can be used to replace a substantial part or greater part of the ethylene oxide, or propylene oxide, or both. Such compounds can be converted into various derivatives of the kind previously described. Under such circumstances, a reaction with glycide and an end reactant to supply a terminal radical is not considered as forming a derivative, but as simply forming the end material. lhe ester and similar derivatives so obtained from the four-component original system, i. e., the ones including glycide, are also veri efiectivefor dem'ulsification ofwate'r in-oil emulsions, as found in theloil industry.

1. A process for breaking petroleum emulsions of the water-in-oiltype, characterized by subjecting the emulsion to the action of a demulsifier includin a cogeneric mixture of a homologous 1 0- series;of glycol ethers of alpha-terpineol;.; said cogeneric mixture being derived exclusively from;

alpha-terpineol, ethylene oxide and propylene oxide in such weight proportions so the average composition of said cogeneric mixture stated in terms of initial reactants lies approximately within the segment of the circle of the accompanying drawing in which the minimum alphaterpineol content is at least 4% and which circle is identified by the fact that points I, 3 and 6 lie on its circumference, and with the proviso that the alpha-terpineol be reacted first with all the propylene oxide and then with the ethylene oxide.

2. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifier including a cogeneric mixture of a homologous series of glycol ethers of alpha-terpineol; said cogeneric mixture being derived exclusively from alpha-terpineol, ethylene oxide and propylene oxide in such weight proportions so the average composition of said. cogeneric mixture stated in terms of initial reactants lies approximately within the triangular area defined in the accompanying drawing by points I, 3 and 6, and with the proviso that the alpha-terpineol be reacted first with all the propylene oxide and then with the ethylene oxide.

3. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifier including a cogeneric mixture of a homologous series of glycol ethers of alpha-terpineol; said cogeneric mixture being derived exclusively from alpha-terpineol, ethylen oxide and propylene oxide in such Weight proportions so the average composition of said cogeneric mixture stated in terms of initial reactants lies approximately within the triangular area defined in the accompanying drawing by points 2, 4 and 5, and with the proviso that the alpha-terpineol be reacted first with all the propylene oxide and then with the ethylene oxide.

4. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifier including a cogeneric mixture of a homologous series of glycol ethers of alpha-terpineol; said cogeneric mixture being derived exclusively from alpha-terpineol, ethylene oxide and propylene oxide in such weight proportions so the average composition of said cogeneric mixture stated in terms of initial reactant lies approximately at point I in the accompanying drawing, and with the proviso that the alpha-terpineol be reacted first with all the propylene oxide and then with the ethylene oxide.

5. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifier including a single cogeneric mixture of a homologous series of glycol ethers of alpha-terpineol; said cogeneric mixture being derived exclusively from alpha-terpineol, ethylene oxide and propylene oxide in such weight proportions so the average composition of said cogeneric mixture stated 2,549,431" 19; 2o: interms ofi initial reactants lies approximately at UNITED STATES PATENTS point I in the accompanying drawing, and with Numb Na 1 the proviso that the alpha-terpineol be reacted 3 me Date De Gr ot a Fe 1941 first wlth. all the propylene made and then with 2 243330 De g g BE g 1941 the ethylene 8 2 307 058 Moeller m" Jan 5 1943 MELVIN DE GROOTE- 2,317,726 Boedeker et a1 Apr. 27: 1943 ARTHUREWIRTEL 2,330,474 De Groote Sept. 28, 1943 REF R OWEN HPETTINGHL- 2,440,093 Israel V Apr. 20, 1948 E E CITED 2,481,278 Ballardetal'. Sept. 6, 1949 The following references are of record in the m file of this patent: 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE, CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER INCLUDING A COGENERIC MIXTURE OF A HOMOLOGOUS SERIES OF GLYCOL ETHERS OF ALPHA-TERPINEOL; SAID COGENERIC MIXTURE BEING DERIVED EXVLUSIVELY FROM ALPHA-TERPINEOL, ETHYLENE OXIDE AND PROPYLENE OXIDE IN SUCH WEIGHT PROPORTIONS SO THE AVERAGE COMPOSITION OF SAID COGENERIC MIXTURE STATED IN TERMS OF INITIAL REACTANTS LIES APPROXIMATELY WITHIN THE SEGMENT OF THE CIRCLE OF THE ACCOMPANYING DRAWING IN WHICH THE MINIMUM ALPHATERPINEOL CONTENT IS AT LEAST 4% AND WHICH CIRCLE IS IDENTIFICED BY THE FACT THAT POINTS 1,3 AND 6 LIE ON ITS CIRCUMFERENCE, AND WITH THE PROVISO THAT 